Oxidizing hair coloring agents containing 2,5-diamino-1-phenylbenzene derivatives and novel 2,5-diamino-1-phenylbenzene derivatives

ABSTRACT

The object of the present patent application are agents for the oxidative coloring of keratin fibers, particularly hair, based on a developer-coupler combination, characterized in that they contain as the developer at least one 2,5-diamino-1-phenylbenzene derivative of general formula                    
     and novel 2,5-diamino-1-phenylbenzene derivatives of formula (I) wherein at least one of the R1 to R10 radicals is different from hydrogen.

The present invention relates to agents for oxidative coloring ofkeratin fibers, particularly human hair, based on a developer/couplercombination and which contain as the developer a2,5-diamino-1-phenylbenzene derivative and to novel2,5-diamino-1-phenylbenzene derivatives.

Oxidation dyes have become very important for the coloring of keratinfibers, particularly in the field of hair coloring. In this case, thecolor is created by reaction of certain developers with certain couplersin the presence of an appropriate oxidant. Suitable developers for thispurpose are, in particular, 2,5-diaminotoluene, 2,5-diaminophenylethylalcohol, p-aminophenol and 1,4-diaminobenzene. Suitable couplers are,for example, resorcinol 4-chlororesorcinol, 1-naphthol, 3 aminophenoland derivatives of m-phenylenediamine.

Oxidation dyes used for coloring human hair must meet many specialrequirements besides producing colorations of a desired intensity. Thedyes must be toxicologically and dermatologically harmless, and theresulting hair colors must have good light, permanent wave, acid andrubbing resistance. The hair colors must also remain stable for a periodof at least four to six weeks in the absence of light, rubbing andchemicals. In addition, it must be possible, by means of a combinationof appropriate developers and couplers, to create a wide range ofdifferent color shades.

Currently used coloring agents, however, do not meet the aforesaidrequirements in all respects.

Hence, a need continues to exist for novel developers which will meetthe aforesaid requirements to a high degree.

In this regard, we have now found that 1,4-diaminobenzene derivatives ofgeneral formula (I) meet the requirements placed on developer componentsto an unusually high degree. Thus, by use of such developer componentstogether with known coupler components, intense color shades areobtained which are unusually resistant to light and washing.

The object of the present invention are agents for oxidative coloring ofkeratin fibers, for example wool, furs, feathers or hair, particularlyhuman hair, based on a developer-coupler combination containing as thedeveloper a 2,5-diamino-1-phenylbenzene derivative of general formula(I)

wherein

R1, R2, R3 and R4 independently of each other denote hydrogen, a C₁-C₆alkyl, C₁-C₄ hydroxyalkyl, C₂-C₄ dihydroxyalkyl or C₁-C₄alkoxy-(C₁-C₄)alkyl group, or R1 and R2 or R3 and R4 form afour-membered to eight-membered aliphatic ring, with at least two of theR1 to R4 groups denoting hydrogen;

R5 denotes hydrogen, a hydroxyl group, a halogen atom or a C₁-C₄ alkyl,C₁-C₄ hydroxyalkyl or C₁-C₄ alkoxy group;

R6, R7, R8, R9 and R10 independently of each other denote hydrogen, ahalogen atom or a cyano, hydroxyl, C₁-C₄ alkoxy, C₁-C₈ alkyl, C₁-C₄alkyl thioether, mercapto, nitro, amino, alkylamino, dialkylamino,trifluoromethane, —C(OH), —C(O)CH₃, —C(O)CF₃, —Si(CH₃)₃, C₁-C₄hydroxyalkyl, C₁-C₄ dihydroxyalkyl, —CH═CHR11 or —(CH₂)_(p)—CO₂R12 groupor a —(CH₂)_(p)—R13 group, where p=1, 2, 3 or 4, or a —C(R14)═NR15 groupor a C(R17)H—NR18R19 group, or two adjacent R6 to R10 groups form a—O—CH₂—O bridge;

R11 denotes hydrogen, a hydroxyl, nitro, amino, CO₂R12 or —C(O)CH₃group;

R12, R14 and R17 independently od each other denote hydrogen or a C₁-C₄alkyl group;

R13 denotes an amino or nitrile group;

R15, R18 and R19 independently of each other denote hydrogen, ahydroxyl, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl or C₃-C₄ dihydroxyalkyl groupor a radical of formula

R16 denotes hydrogen, an amino group or a hydroxyl group,

or containing a the physiologically tolerated, water-soluble saltthereof.

Suitable compounds of formula (I) are, for example:

2,5-diamino-1-phenylbenzene; 2,5-diamino-1-(4-bromophenyl)benzene;2,5-diamino-1-phenyl-1-(4-ethenylphenyl)benzene;2,5-diamino-1-(2,3,4-trimethoxyphenyl)benzene;2,5-diamino-1-[2,4-di(2-hydroxyethyl)aminophenyl]benzene;2,5-diamino-1-(2,4-diaminophenyl)benzene;2,5-diamino-1-(2,4-dihydroxyphenyl)benzene;2,5-diamino-1-(2,4-dimethylaminophenyl)benzene;2,5-diamino-1-(2,4-methoxyphenyl)benzene;2,5-diamino-1-[2,5-di(2-hydroxyethyl)aminophenyl]benzene;2,5-diamino-1-(2,5-diaminophenyl)benzene;2,5-diamino-1-(2,5-dihydroxyphenyl)benzene;2,5-diamino-1-(2,5-dimethoxyphenyl)benzene;2,5-diamino-1-(2,5-dimethylaminophenyl)benzene;2,5-diamino-1-[2,6-di(2-hydroxyethyl)aminophenyl;2,5-diamino-1-(2,6-diaminophenyl]benzene;2,5-diamino-1-(2,6-dihydroxyphenyl)benzene;2,5-diamino-1-(2,6-dimethoxyphenyl)benzene;2,5-diamino-1-(2,6-dimethylaminophenyl)benzene;2,5-diamino-1-[2-(bromomethyl)phenyl]benzene;2,5-diamino-1-(2-amino-5-hydroxyphenyl)-benzene;2,5-diamino-1-(2-aminophenyl)benzene;2,5-diamino-1-(2-carboxyphenyl)benzene;2,5-diamino-1-(2-chlorophenyl)benzene;2,5-diamino-1-[2-di(2-hydroxyethyl)aminophenyl]benzene;2,5-diamino-1-(2-dimethylaminophenyl)benzene;2,5-diamino-1-(2-fluorophenyl)benzene;2,5-diamino-1-(2-formylphenyl)benzene;2,5-diamino-1-(2-hydroxy-4-aminophenyl)benzene;2,5-diamino-1-(2-hydroxy-5-aminophenyl)benzene;2,5-diamino-1-(2-hydroxyphenyl)benzene;2,5-diamino-1-(2-methoxyphenyl)benzene;2,5-diamino-1-(2-methylphenyl)benzene;2,5-diamino-1-(2-nitrophenyl)benzene;2,5-diamino-1-(2-trifluoromethylphenyl)benzene;2,5-diamino-1-[3,5-di(2-hydroxyethyl)aminophenyl]benzene;2,5-di-amino-1-(3,5-diaminophenyl)benzene;2,5-diamino-1-(3,5-dihydroxyphenyl)benzene;2,5-diamino-1-(3,5-dihydroxyphenyl)benzene;2,5-diamino-1-(3,5-dimethylaminophenyl)benzene;2,5-diamino-1-(3-aminophenyl)benzene;2,5-diamino-1-(3-bromophenyl)benzene;2,5-diamino-1-(3-carboxyphenyl)benzene;2,5-diamino-1-(3-chlorophenyl)benzene;2,5-diamino-1-[3-di(2-hydroxyethyl)aminophenyl]benzene;2,5-diamino-1-(3-dimethylaminophenyl)benzene;2,5-diamino-1-(3-fluorophenyl)benzene;2,5-diamino-1-(3-formylphenyl)benzene;2,5-diamino-1-(3-hydroxy-5-aminophenyl)benzene;2,5-diamino-1-(3-hydroxy-phenyl)benzene;2,5-diamino-1-(3-methoxyphenyl)benzene;2,5-diamino-1-(3-nitrophenyl)benzene;2,5-diamino-1-(3-fluoromethylphenyl)benzene;2,5-diamino-1-[4-(dimethylamino)phenyl]benzene;2,5-diamino-1-[4-(hydroxymethyl)phenyl]benzene;2,5-diamino-1-[4-(methylthio)phenyl]benzene;2,5-diamino-1-[4-(trifluoromethyl)phenyl]benzene;2,5-diamino-1-[4-(trimethylsilyl)phenyl]benzene;2,5-diamino-1-(4-acetylphenyl)benzene;2,5-diamino-1-(4-aminophenyl)benzene;2,5-diamino-1-(4-carboxyphenyl)benzene;2,5-diamino-1-(4-chlorophenyl)benzene;2,5-diamino-1-[4-(di(2-hydroxyethyl)aminophenyl]benzene;2,5-diamino-1-(4-dimethylaminophenyl)benzene;2,5-diamino-1-(4-ethoxyphenyl)benzene;2,5-diamino-1-(4-fluorophenyl)benzene;2,5-diamino-1-(4-formylphenyl)benzene;2,5-diamino-1-(4-hydroxyphenyl)benzene;2,5-diamino-1-(4-methoxyphenyl)benzene;2,5-diamino-1-(4-methylphenyl)benzene; 2,5-diamino-1-phenylbenzene;2,5-diamino-4-chloro-1-phenylbenzene;2,5-diamino-4-methoxy-1-phenylbenzene;2,5-diamino-4-methyl-1-phenylbenzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2,4-dihydroxyphenyl)-benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2,5-diaminophenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2,6-dimethoxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2-amino-5-hydroxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2-aminophenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2-hydroxy-4-aminophenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2-hydroxy-5-aminophenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2-hydroxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)-1-(2-methoxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(2-methylphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)-amino-1-(3,5-diaminophenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(3,5-dihydroxy-phenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(3-aminophenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(3-hydroxy-5-aminophenyl)-benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(3-hydroxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(3-methoxyphenyl)benzene;2,5-diamino-1-(3-nitrophenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-[4-dimethylamino)phenyl]benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-[4-(trifluoromethyl)phenyl]benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(4-aminophenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(4-carboxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(4-carboxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(4-hydroxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(4-methoxyphenyl)benzene;2-amino-5-(2,3-dihydroxypropyl)amino-1-(4-methylphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2,4-diaminophenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2,4-dihydroxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2,5-diaminophenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2,5-dimethoxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2,6-dimethoxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2-amino-5-hydroxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2-aminophenyl)benzene;2-amino-5-(2-hydroxyethyl(amino-1-(2-hydroxy-4-aminophenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2-hydroxy-5-aminophenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2-hydroxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2-hydroxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(2-methylphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(3,5-diaminophenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(3,5-dihydroxyphenyl)benzene2-amino-5-(2-hydroxyethyl)amino-1-(3-aminophenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(3-hydroxy-5-aminophenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(3-hydroxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(3-methoxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-[4-(dimethylamino)phenyl]benzene;2-amino-5-(2-hydroxyethyl)amino-1-[4-(trifluoromethyl)phenyl]benzene;2-amino-5-(2-hydroxyethyl)amino-1-(4-aminophenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(4-carboxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(4-chlorophenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(4-hydroxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(4-methoxyphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-(4-methylphenyl)benzene;2-amino-5-(2-hydroxyethyl)amino-1-phenylbenzene;2-amino-5-(2-methoxyethyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2,4-diaminophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2,4-dihydroxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2,5-diaminophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2,5-dimethoxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2,6-dimethoxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2-amino-5-hydroxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2-aminophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2-hydroxy-4-aminophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2-hydroxy-5-aminophenyl)-benzene;2-amino-5-(2-methoxyethyl)amino-1-(2-hydroxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2-methoxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2-methylphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(3,5-diaminophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(3,5-dihydroxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(3-aminophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(3-hydroxy-5-aminophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(2-hydroxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(3-methoxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-[4-(dimethylamino)phenyl])benzene;2-amino-5-(2-methoxyethyl)amino-1-[4-(trifluoromethyl)phenyl])benzene;2-amino-5-(2-methoxyethyl)amino-1-(4-aminophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(4-carboxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(4-chlorophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(4-chlorophenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(4-methoxyphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(4-methylphenyl)benzene;2-amino-5-(2-methoxyethyl)amino-1-(4-methylphenyl)benzene;2-amino-5-(2-m2methoxyethyl)amino-1-phenylbenzene;-amino-5-di-(2-hydroxyethyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2,3-difluorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2,4,6-trimethylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2,4-diaminophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2,4-dichlorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2,4-dihydroxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2,5-diaminophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2,5-dimethoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2,6-difluorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2,6-dimethoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-[(bis(1-methylethyl)amino)carbonyl]phenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-[(bis(1-methylethyl)amino)carbonyl]-3-methoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)-amino-1-(2-(bromomethyl)phenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-[2-(diethylamino)carbonyl]phenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-amino-5-hydroxy-phenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-amino phenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-carboxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-chlorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-fluorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-formyl-4-methoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-formyl-4-methylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-formyl-5-methoxy-phenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-formylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-hydroxy-4-aminophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-hydroxy-5-aminophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-hydroxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-methoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-methylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-nitrophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(2-trifluoromethylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3,4-dichlorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3,5-diaminophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3,5-dichlorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3,5-dihydroxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-acetylaminophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-aminophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-bromophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-carboxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-chloro-4-fluorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-chlorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-fluorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-formylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-hydroxy-5-aminophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-hydroxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-methoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-methylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-nitrophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(3-trifluoromethylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-[4-(bromomethyl)phenyl]benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-[4-(dimethylamino)phenyl]benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-[4-(hydroxymethyl)phenyl]benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-[4-(methylthio)phenyl]benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-[4-(trifluoromethyl)phenyl]benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-[4-(trimethylsilyl)phenyl]benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-acetylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-aminophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-bromophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-carboxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-chloro-3-methoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-chlorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-ethenylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-fluorophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-formylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-hydroxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-iodophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-methoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-methyl-3-nitrophenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(4-methylphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(5-bromo-2-methoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-chloro-2-methoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-(5-formyl-2-methoxyphenyl)benzene;2-amino-5-di-(2-hydroxyethyl)amino-1-phenylbenzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2,3-difluoro-4-heptylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2,3-difluorophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2,4,6-trimethylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2,4-diaminophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2,4-dichlorophenyl)benzene;2-amino-5-di-(2-methoxyethyl)-amino-1-(2,4-dihydroxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2,5-dimethoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2,6-difluorophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2,6-dimethoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-[(bis(1-methylethylaminocarbonyl)phenyl]benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-bromomethylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-(diethylaminocarbonylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-carboxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-chlorophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-fluorophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-formyl-4-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-formyl-4-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-formyl-5-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-formylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-formylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-hydroxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-nitrophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(2-trifluoromethylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3,4-dichlorophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3,5-diaminophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3,5-dichlorophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3,5-dihydroxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-[3-(acetylamino)phenyl]benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3-aminophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-[3-bromophenyl]benzene;2-amino-5-di-(2-methoxyethyl)amino-1-[3-carboxyphenyl]benzene;2-amino-5-di-(2-methoxyethyl)amino-1-[3-chloro-4-fluorophenyl]benzene;2-amino-5-di-(2-methoxyethyl)amino-1-[3-chlorophenyl]benzene;2-amino-5-di-(2-methoxyethyl)amino-1-[3-fluorophenyl]benzene;2-amino-5-di-(2-methoxyethyl)amino-1-[3-formylphenyl]benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3-hydroxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3-methylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3-nitrophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(3-trifluoromethylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-bromomethylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-dimethylaminophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-hydroxymethylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-methylthiophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-trifluoromethylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-trimethylsilylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-acetylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-aminophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-carboxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-chloro-3-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-chlorophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-ethoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-ethoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-fluorophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-formylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-hydroxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-iodophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-methyl-3-nitrophenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(4-methylphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(5-brono-2-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(5-chloro-2-methoxyphenyl)benzene;2-amino-5-di-(2-methoxyethyl)amino-1-(5-formyl-2-methoxyphenyl)benzene;2-amino-5-dimethylamino-1-phenylbenzene;2-amino-5-methyl-amino-1-(2,3,4-trimethoxy-phenyl)benzene;2-amino-5-methylamino-1-(2,4-diaminophenyl)benzene;2-amino-5-methylamino-1-(2,4-dihydroxyphenyl)benzene;2-amino-5-methylamino-1-(2,5-diaminophenyl)benzene;2-amino-5-methylamino-1-(2,5-dimethoxyphenyl)benzene;2-amino-5-methylamino-1-(2,6-dimethoxyphenyl)benzene;2-amino-5-methylamino-1-(2-amino-5-hydroxyphenyl)benzene;2-amino-5-methylamino-1-(2-aminophenyl)benzene;2-amino-5-methylamino-1-(2-hydroxy-4-aminophenyl)benzene;2-amino-5-methylamino-1-(2-hydroxy-5-aminophenyl)benzene;2-amino-5-methylamino-1-(2-hydroxyphenyl)benzene;2-amino-5-methylamino-1-(2-methoxyphenyl)benzene;2-amino-5-methylamino-1-(2-methylphenyl)benzene;2-amino-5-methylamino-1-(3,5-diaminophenyl)benzene;2-amino-5-methylamino-1-(3,5-dihydroxyphenyl)benzene;2-amino-5-methylamino-1-(3-aminophenyl)bezene;2-amino-5-methylamino-1-(3-hydroxy-5-aminophenyl)benzene;2-amino-5-methylamino-1-(3-hydroxyphenyl)benzene;2-amino-5-methylamino-1-(3-methoxyphenyl)benzene;2-amino-5-methylamino-1-(4-dimethylaminophenyl)benzene;2-amino-5-methylamino-1-(4-trifluoromethylphenyl)benzene;2-amino-5-methylamino-1-(4-carboxyphenyl)benzene;2-amino-5-methylamino-1-(4-chlorophenyl)benzene;2-amino-5-methylamino-1-(4-hydroxyphenyl)benzene;2-amino-5-methylamino-1-(4-methoxyphenyl)benzene;2-amino-5-methylamino-1-(4-methylphenyl)benzene;2-amino-5-methylamino-1-phenylbenzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-bromophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-ethenylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-[2,4-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,4-diaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,4-dihydroaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,4-dimethylaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,4-di-methoxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-[2,5-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,5-dimethoxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,5-dihydroxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,5-diaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,5-dimethylaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-[2,6-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-[2,6-di-aminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,6-dihydroxyphenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,6-dimethoxyphenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2,6-dimethylaminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-bromomethylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-amino-5-hydroxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-amino-5-hydroxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-aminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-carboxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-chlorophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1[di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-dimethylaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-fluorophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-formylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-hydroxy-4-aminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-hydroxy-5-aminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-hydroxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-methoxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-methylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-nitrophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(2-trifluoromethylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-[3,5-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3,5-diaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3,5-dihydroxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3,5-dimethoxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3,5-dimethylaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-aminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-bromophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-carboxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-chlorophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-[3-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-dimethylaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-fluorophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-formylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-hydroxy-5-aminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-hydroxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-methoxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-nitrophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(3-trifluoromethylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-dimethylaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-hydroxymethylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-methylthiophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-trifluoromethylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-trimethylsilylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-acetylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-aminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-carboxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-chlorophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-[4-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-dimethylaminophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-ethoxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-fluorophenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-formylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-hydroxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-methoxyphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-(4-methylphenyl)benzene;5-amino-2-(2,3-dihydroxypropyl)amino-1-phenylbenzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-bromophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-ethenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-[2,4-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,4-diaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,4-dihydroxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,4-dimethylaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,4-dimethoxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-[2,5-di-(2-hydroxyethyl(aminophenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,5-diaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,5-dihydroxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,5-dimethoxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,5-dimethylaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-[2,6-di-(2-hydroxyethyl(aminophenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,6-diaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,6-dihydroxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-(2,6-dimethoxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2,6-dimethylaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-bromomethylphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-amino-5-hydroxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-aminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-carboxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-chlorophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-[2-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-dimethylaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-fluorophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-formylphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-hydroxy-4-aminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-hydroxy-5-aminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-hydroxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-methoxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-methylphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-nitrophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(2-trifluoromethylphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-[3,5-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3,5-diaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3,5-dihydroxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3,5-dimethoxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3,5-dimethylaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-aminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-bromophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-carboxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-chlorophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-[3-(di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-dimethylaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-fluorophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-formylphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-hydroxy-5-aminophenyl)benzene;5-amino-2-(2-hydroxyethyl(amino-1-(3-hydroxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-methoxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-nitrophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(3-trifluoromethylphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-[4-(dimethylamino)phenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-[4-hydroxymethyl)phenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-[4-(methylthio)phenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-[4-(trifluoromethyl) phenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-[4-(trimethylsilyl)phenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-acetylphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-aminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-carboxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-chlorophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-[4-di-(2-hydroxyethyl)aminophenyl]benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-dimethylaminophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-ethoxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-fluorophenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-formylphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-hydroxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-methoxyphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-(4-methylphenyl)benzene;5-amino-2-(2-hydroxyethyl)amino-1-phenylbenzene;5-amino-2-(2-methoxyethyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2,4-diamino-phenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2,4-dihydroxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2,5-diaminophenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2,5-dimethoxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2,6-dimethoxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2-amino-5-hydroxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2-aminophenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2-hydroxy-4-aminophenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2-hydroxy-5-aminophenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2-hydroxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2-methoxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2-methylphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(2-methoxyethyl)amino-1-(3,5-diaminophenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(3,5-dihydroxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(3-aminophenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(3-hydroxy-5-aminophenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(3-hydroxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(3-methoxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-[4-dimethylamino)phenyl]benzene;5-amino-2-(2-methoxyethyl)amino-1-[4-(trifluoromethyl)phenyl]benzene;5-amino-2-(2-methoxyethyl)amino-1-(4-aminophenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(4-carboxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(4-chlorophenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(4-hydroxyphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(4-methylphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-(4-methylphenyl)benzene;5-amino-2-(2-methoxyethyl)amino-1-phenylbenzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,3-difluoro-4-heptylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,3-difluorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,4,6-trimethylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,4-diaminophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,4-dichlorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,4-dihydroxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,5-dimethoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,6-difluorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2,6-dimethoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-[(bis(1-methylethyl)amino)carbonyl)phenyl]benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-[(bis(1-methylethyl)amino)carbonyl)-3-methoxyphenyl]benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-bromomethylphenyl)benzene;5-amino-di(2-hydroxyethyl)amino-1-(2-diethylaminocarbonyl)phenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-carboxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-chlorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-fluorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-formyl-4-methoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-formyl-4-methylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-formyl-5-methoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-formylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-hydroxy-4-aminophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-hydroxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-methoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-methylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-nitrophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(2-trifluoromethylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3,4-dichlorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3,5-diaminophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3,5-dichlorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3,5-dihydroxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-acetylaminophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-aminophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-bromophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-carboxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-chloro-4-fluorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-chlorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-fluorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-formylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-hydroxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-methoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-methylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-nitrophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(3-trifluoromethylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-(bromomethylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-dimethylaminophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-hydroxymethylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-methylthiophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-trifluoromethylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-trimethylsilylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-acetylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-aminophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-bromophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-carboxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-chloro-3-methoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-chlorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-ethenylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-ethoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-fluorophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-formylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-hydroxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-iodophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-methoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-methyl-3-nitrophenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(4-methylphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(5-bromo-2-methoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(5-chloro-2-methoxyphenyl)benzene;5-amino-2-di(2-hydroxyethyl)amino-1-(5-formyl-2-methoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,3,4-trimethoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,3-difluoro-4-heptylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,3-difluorophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,4,6-trimethylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,4-diaminophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,4-dichlorophrnyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,4-dihydroxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,5-dimethoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,6-difluorophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2,6-dimethoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-[(bis(1-methylethylaminocarbonyl)phenyl]benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-[(bis(1-methylethylaminocarbonyl)-3-methoxyphenyl]benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-bromomethylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-[2-(diethylaminocarbonyl)phenyl]benzene;5-amino-2-di(2-methoxyethyl)amino-1-[2-carboxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-[2-chlorophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-fluorophenyl)benzene;5-amino-2-di]-(2-methoxyethyl)amino-1-(2-formyl-4-methoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-formyl-4-methylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-formyl-5-methoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-formylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-hydroxy-4-aminophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-hydroxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-methoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-methylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-nitrophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(2-trifluoromethylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3,4-dichlorophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3,5-diaminophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3,5-dichlorophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3,5-dihydroxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-acetylaminophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-aminophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-bromophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-carboxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-chloro-4-fluorophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-chlorophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-fluorophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-formylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-hydroxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-methoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-methylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-nitrophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(3-trifluoromethylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-bromomethylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-dimethylaminophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-hydroxymethylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-methylthiophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-trifluoromethylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-trimethylsilylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-acetylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-aminiphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-bromophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-carboxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-chloro-3-methoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-chlorophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-ethenylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-ethoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-formylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-hydroxymethylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-iodophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-methoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-methyl-3-nitrophenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(4-methylphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(5-bromo-2-methoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(5-chloro-2-methoxyphenyl)benzene;5-amino-2-di(2-methoxyethyl)amino-1-(5-formyl-2-methoxyphenyl)benzene;5-amino-2-dimethylamino-1-phenylbenzene;5-amino-2-methylamino-1-(2,3,4-trimethoxyphenyl)benzene;5-amino-2-methylamino-1-(2,4-diaminophenyl)benzene;5-amino-2-methylamino-1-(2,4-dihydroxyphenyl)benzene;5-amino-2-methylamino-1-(2,5-diaminophenyl)benzene;5-amino-2-methylamino-1-(2,5-dimethoxyphenyl)benzene;5-amino-2-methylamino-1-(2,6-dimethoxyphenyl)benzene;5-amino-2-methylamino-1-(2-amino-5-hydroxyphenyl)benzene;5-amino-2-methylamino-1-(2-aminophenyl)benzene;5-amino-2-methylamino-1-(2-hydroxy-4-aminophenyl)benzene;5-amino-2-methylamino-1-(2-hydroxy-5-aminophenyl)benzene;5-amino-2-methylamino-1-(2-hydroxyphenyl)benzene;5-amino-2-methylamino-1-(2-methoxyphenyl)benzene;5-amino-2-methylamino-1-(2-methylphenyl)benzene;5-amino-2-methylamino-1-(3,5-diaminophenyl)benzene;5-amino-2-methylamino-1-(3,5-dihydroxyphenyl)benzene;5-amino-2-methylamino-1-(3-aminophenyl)benzene;5-amino-2-methylamino-1-(3-hydroxy-5-aminophenyl)benzene;5-amino-2-methylamino-1-(3-hydroxyphenyl)benzene;5-amino-2-methylamino-1-(3-methoxyphenyl)benzene;5-amino-2-methylamino-1-(4-dimethylaminophenyl)benzene;5-amino-2-methylamino-1-(4-trifluoromethylphenyl)benzene;5-amino-2-methylamino-1-(4-aminophenyl)benzene;5-amino-2-methylamino-1-(4-carboxyphenyl)benzene;5-amino-2-methylamino-1-(4-chlorophenyl)benzene;5-amino-2-methylamino-1-(4-hydroxyphenyl)benzene;5-amino-2-methylamino-1-(4-methoxyphenyl)benzene;5-amino-2-methylamino-1-(4-methylphenyl)benzene and5-amino-2-methylamino-1-phenylbenzene.

Preferred are compounds of formula (I) wherein (i) R1 and R2 or R3 andR4 or all radicals from R1 to R4 denote hydrogen and/or (ii) four ofradicals R6 to R10 represent hydrogen and the fifth radical denoteshydrogen or a —C(OH)H, —C(O)CH₃, C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl groupand/or (iii) R5 denotes hydrogen.

Particularly well suited 2,5-diamino-1-phenylbenzene derivatives offormula (I) in terms of the overall invention are2,5-diamino-1-phenylbenzene; 2,5-diamino-1-(3-nitrophenyl)benzene;2,5-diamino-1-(4-methoxyphenyl)benzene;2,5-diamino-1-(3-aminophenyl)benzene;2,5-diamino-1-(2-methylphenyl)benzene;2,5-diamino-1-(3-methylphenyl)benzene;2,5-diamino-1-(4-methylphenyl)benzene;2,5-diamino-1-(3-chlorophenyl)benzene and2,5-diamino-1-(4-chlorophenyl)benzene or the physiologically toleratedsalts thereof.

The compounds of formula (I) can be used as free bases or in the form oftheir physiologically tolerated salts with inorganic or organic acidssuch as, for example, hydrochloric, sulfuric, phosphoric, acetic,propionic, lactic or citric acid.

The colorants of the invention contain the 2,5-diamino-1-phenylbenzenederivative of formula (I) in an amount from about 0.005 to 20 wt %, anamount from about 0.01 to 5.0 wt % and particularly from 0.1 to 2.5 wt %being especially preferred.

Suitable couplers are preferably 2,6-diaminopyridine,2-amino-4-[(2-hydroxyethyl)amino]anisole,2,4-diamino-1fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene, 2,4-di-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxypyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxpyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,3-[(2-aminoyethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane,di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis(2-hydroxyethyl)aminotoluene, 4-hydroxyindole,3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol,5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol,3-aminophenol, 2-[(3-hydroxyphenyl)amino]acetaminde,5-[(2-hydroxyethyl)amino]-2-methylphenol, 3-](2-hydroxyethyl)aminol,3-[(2-methoxyethyl)amino]phenol, 5-amino-2-ethylphenol,2-(4-amino-2-hydroxyphenoxy)ethanol,5-[3-(hydroxypropyl)amino]-2-methylphenol,3-[(2,3-dihydroxypropyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,5-amino-4-chloro-2-methylphenol, 1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,3,4-methylenedioxyphenol, 3,4-methylene dioxyaniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxol,6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxyindo 5,6-dihydroxyindoline, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole and 2,3-indolinedione.

Although the advantageous properties of the diamino benzene derivativesof formula (I) suggest that said derivatives be used as the onlydeveloper, it is, of course, possible to use diaminobenzene derivativesof formula (I) together with other known developers, for example with1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol,4-aminophenol and its derivatives, for example 4-amino-3-methylphenol,4,5-diamino-1-(2-hydroxyethyl)pyranole or a tetraaminopyrimidine.

In the colorant of the invention, the couplers and developers can becontained alone or in admixture with each other, the total amount ofcouplers and developers in the colorant of the invention ranging from0.005 to 20 wt %, preferably from about 0.01 to 5.0 wt % andparticularly from 0.1 to 2.5 wt % (based on the total amount ofcolorant).

The total amount of the developer-coupler combination contained in thecolorants described here is preferably about 0.01 to 20 wt %, an amountfrom about 0.02 to 10 wt % and particularly from 0.2 to 6.0 wt % beingespecially preferred. In general, the developers and couplers are usedin about equimolar amounts. It is not disadvantageous, however, to usethe developer in a certain excess or deficiency, for example in acoupler:developer ratio of 1:2 to 1:0.5.

Moreover, the colorant of the invention can also contain othercomponents, for example 6-amino-2-methylphenol and2-amino-5-methylphenol, as well as common direct dyes, for exampletriphenylmethane dyes such as[(4′-aminophenyl)-(4′-imino-2″,5″-cyclohexadien-1″-ylidene)methyl-2-methylaminobenzemonohydrochloride (C.I. 42510) and4-[(4′-amino-3′-methylphenyl)(4″-imino-3″-methyl-2″,5″-cyclohexadient-1″-yl)idine)methyl]-2-methylaminobenzenemonohydrochloride (C.I.42520), aromatic nitro dyes, such as4-(2′-hydroxyethyl)aminonitrotoluene, 2-amino-4,6-dinitrophenol,2-amino-5-(2′-hydroxyethyl)aminonitrobenzene,2-chloro-6-(ethylamino)-4-nitrophenol,4-chloro-N-(2-hydroxyethyl)-2-nitroaniline,5-chloro-2-hydroxy-4-nitroaniline, 2-amino-4-chloro-6-nitrophenol and1-[(2′-ureidoethyl)amino-4-nitrobenzene, furthermore azo dyes such assodium 6-[(4′aminophenyl])azo]-5-hydroxynaphthalenesulfonate, anddisperse dyes such as, for example 1,4-diaminoanthraquinone and1,4,5,8-tetraaminoanthraquinone. The colorants can contain thesecomponents in an amount from about 0.1 to 4.0 wt %.

Naturally, the couplers and developers as well as the other dyecomponents, if they are bases, can also be used in the form of theirphysiologically tolerated salts with organic or inorganic acids such as,for example, hydrochloric or sulfuric acid, or—if they contain aromaticOH groups—in the form of salts with bases, for example as their alkalimetal phenoxides.

Moreover, the colorants, if they are intended for coloring hair, cancontain other common cosmetic additives, for example antioxidants suchas ascorbic acid, thioglycolic acid or sodium sulfite, as well asperfumes, complexing agents, wetting agents, emulsifiers, thickeners andhair-care agents. The form in which the colorant preparations of theinvention appear can be, for example, that of a solution, particularlyan aqueous or aqueous-alcoholic solution. Particularly preferredpreparation forms, however, are creams, gels or emulsions. Theircomposition consists of a mixture of dye components and the usualadditives for such preparations.

Conventional additives to solutions, creams, emulsions or gels are, forexample, solvents such as water, the lower aliphatic alcohols, forexample ethanol, propanol or isopropanol, glycerol or glycols such as1,2-propylene glycol, moreover wetting agents or emulsifiers from theclass of anionic, cationic, amphoteric or nonionic surfactants, such asfatty alcohol sulfates, ethoxylated fatty alcohol sulfates,alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts,alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols,fatty alkanolamides, ethoxylated fatty esters, furthermore thickeners,such as the fatty alcohols, starch or cellulose derivatives, furthermorevaseline, paraffin oil and fatty acids as well as hair-care agents suchas cationic resins, lanolin derivatives, cholesterol, pantothenic acidand betaine. The said constituents are employed in amounts normally usedfor such purposes, for example the wetting agents and emulsifiers in anamount from about 0.5 to 30 wt %, the thickeners in an amount from about0.1 to 25 wt % and the hair-care agents at a concentration of about 0.1to 5.0 wt %.

Depending on the composition, the colorant of the invention can beweakly acidic, neutral or alkaline. In particular, it has a pH from 6.8to 11.5, the adjustment to alkaline pH preferably being done withammonia. Organic amines, for example monoethanolamine andtriethanolamine, as well as inorganic bases such as sodium hydroxide andpotassium hydroxide, however, can also be used. Suitable for pHadjustment to an acidic value are inorganic or organic acids, forexample phosphoric, acetic, citric or tartaric acid.

To use the afore-described colorants for oxidative dyeing of hair, saidcolorants are mixed with an oxidant immediately before use, and themixture is applied to hair in an amount sufficient for hair treatmentwhich, depending on hair fullness, is generally from about 60 to 200grams.

Suitable oxidants for developing the hair color are mainly hydrogenperoxide or a compound of addition of hydrogen perbxide to urea,melamine, sodium borate or sodium carbonate, in the form of a 3 to 12%,preferably 6%, aqueous solution, as well as air oxygen. When a 6%hydrogen peroxide solution is used as the oxidant, the weight ratio ofhair colorant to oxidant is 5:1 to 2:1, and preferably 1:1. Largeramounts of oxidant are used primarily when the hair colorant contains ahigher dye concentration or when stronger hair bleaching is desired atthe same time. The mixture is allowed to act on the hair at 15 to 50° C.for about 10 to 45 minutes and preferably for 30 minutes. The hair isthen rinsed with water and dried. Optionally, this rinse can be followedwith a shampoo wash, optionally followed by rinsing with a weak organicacid, for example citric or tartaric acid. The hair is then dried.

The colorant of the invention containing as the developer adiaminobenzene derivative of formula (I) affords colorations ofexcellent color fastness, particularly in terms of light fastness, washfastness and rubbing fastness. As regards the coloring properties, thecolorants of the invention, depending on the type and composition of thedye components, provide a wide range of different color shades rangingfrom brown, purple, violet to blue and black shades. The color intensityof the color shades is particularly good. The very good coloringproperties of the colorants of the present patent application alsomanifest themselves, in particular, in that these colorants make itpossible readily to color with good coverage gray, chemically notpredamaged hair.

The 2,5-diamino-1-phenylbenzene derivatives of formula (I) are readilywater-soluble affording colorations of high color intensity andoutstanding color fastness, particularly as regards light fastness, washfastness and rubbing fastness. Moreover, they show excellent storagestability, particularly as components of the aforedescribed colorants.

Another object of the present invention are novel2,5-diamino-1-phenylbenzene derivatives of formula (I) or thephysiologically tolerated water-soluble salts thereof, water-solublesalts wherein at least one of radicals R1 to R10 is different fromhydrogen.

The 2,5-diamino-1-phenylbenzene derivatives of formula (I) can beprepared by known synthetic methods, for example by the methodsdescribed in the following practical examples.

The following examples are intended to further illustrate the object ofthe invention without limiting it to these examples.

EXAMPLES Example 1 Synthesis of 2,5-Diamino-1-Phenylbenzene Derivativesof Formula (I) (General Method of Synthesis)

A. Synthesis of 2,5-tert.Butylcarbonylaminobromobenzene

15.65 g (0.07 mole) of bromo-p-phenylenediamine hydrochloride and 32.7 g(0.15 mole) of ditert.butyl dicarbonate were dissolved in a mixture of250 mL of 2 N sodium hydroxide and 250 mL of trifluorotoluene, and theresulting mixture was heated to 45° C. The reaction mixture was allowedto agitate for 3 days. An additional 30 g (0.14 mole) of ditert.butyldicarbonate was added stepwise. The organic layer was then separated,and the aqueous phase was extracted twice with 100-mL portions ofdichloromethane. The combined extracts were evaporated, and the residuewas taken up in 200 mL of hexane. The precipitate was filtered off andwashed with 50 mL of hexane.

This gave 18.6 g (82% of the theoretical) of2,5-tert.butylcarbonylaminobromobenzene with a melting point at 130° C.

B. Synthesis of 2,5-Diamino-1-phenylbenzene derivatives of Formula (I)

3.3 g (0.01 mole) of 2,5-tert.butyloxycarbonylaminobromobenzene fromstep A and 0.013 mole of the desired boric acid derivative weredissolved in 70 mL of 1,2-dimethoxyethane under argon. Then, 0.5 g oftetrakis(triphenylphosphine)palladium (0.0005 mole) and 13 mL of 2 Npotassium carbonate solution were added, the reaction mixture was pouredinto 100 mL of ethyl acetate. The organic phase was extracted withdilute sodium hydroxide solution and then dried over magnesium sulfate.The solvent was distilled off from a rotary evaporator and the residuewas purified [by column chromatography] on silica gel using petroleumether/ethyl acetate (9:1) [for elution]. The resulting product wasdissolved in 40 mL of ethanol and the solution was heated to 50° C.

To prepare the hydrochloride, 15 mL of a 2.9 molar ethanolichydrochloric acid solution was added dropwise. The precipitate wasfiltered off, washed twice with 10-mL portions of ethanol and dried.

a) 2,5-Diamino-1-phenylbenzene Dihydrochloride

Boric acid used: phenylboric acid

Yield: 1.8 g (72% of the theoretical)

Melting point: 250° C. (colorless crystals).

CHN analysis (C₁₂H₁₄N₂Cl₂ % C % H % N Calcd. 56.06 5.49 10.89 Found55.95 5.46 10.58

b) 2,5-Diamino-1-(3-nitrophenyl)benzene Dihydrochloride

Boric acid used: 3-nitrophenylboric acid

Yield: 1.9 g (65% of the theoretical)

Melting point: 245° C. (colorless crystals).

CHN analysis (C₁₂H₁₃N₃O₂Cl₂) % C % H % N Calcd. 47.70 4.34 13.91 Found47.89 4.28 13.78

c) 2,5-Diamino-(1-3-methoxyphenyl)benzene Dihydrochloride

Boric acid used: 3-methoxyphenylboric acid

Yield: 2.01 g (72% of the theoretical)

Melting point: 255° C. (colorless crystals).

CHN analysis (C₁₃H₁₆N₂OCl₂) % C % H % N Calcd. 54.37 5.62 9.75 Found54.25 5.59 9.60

d) 2,5-Diamino-1-(4-methoxyphenyl)benzene Dihydrochloride

Boric acid used: 4-methoxyphenylboric acid

Yield: 2.2 g (77% of the theoretical)

Melting point: 250° C. (colorless crystals).

CHN analysis (C₁₃H₁₆N₂OCl₂) % C % H % N Calcd. 54.37 5.62 9.75 Found54.51 5.32 9.64

e) 2,5-Diamino-1-(3-aminophenyl)benzene Dihydrochloride

Boric acid used: 3-aminophenylboric acid

Yield: 0.6 g (20% of the theoretical)

Melting point: 260° C. (colorless crystals).

CHN analysis (C₁₂H₁₆N₃Cl₃) % C % H % N Calcd. 46.7 5.23 13.61 Found46.47 5.48 11.94

C. Synthesis of N,N′-bis(tert.Butoxycarbonyl)-2,5-diamino-1-phenylboricAcid

N,N′-bis(tert.Butoxycarbonyl)-2,5-diamino-1-phenylboric acid wasprepared by reaction ofN,N′-bis(tert.butoxycarbonyl)-2,5-diamino-1-bromobenzene withtert.butyllithium and trimethyl borate. The experimental procedure forthis method of preparation has been described by J. M. Tour and J. J. S.Lamba in J. Am. Chem. Soc. 116, 11723 (1994).

D. Synthesis of 2,5-Diamino-1-phenylbenzenes

0.035 g (0.0001 mole) of 2,5-tert.butyloxycarbonylamino-1-phenylboricacid from step C and 0.00015 mole of the desired bromo derivative weredissolved in 10 mL of 1,2-dimethoxyethane under argon. Then, 0.005 g oftetrakis(phenylphoshphine)-palladium (0.000005 mole) and 0.13 mL of 2 Npotassium carbonate solution were added, and the reaction mixture washeated to 80° C. At the end of the reaction, the reaction mixture waspoured into 10 mL of ethyl acetate, the organic phase was extracted withdilute sodium hydroxide solution and then dried over magnesium sulfate.The solvent was distilled off from a rotary evaporator, and the residuewas purified [by column chromatography] over silica gel using petroleumether/ethyl acetate (9:1) [as the eluent]. The resulting product wasdissolved in 4-mL of ethanol, and the solution was heated to 50° C.

To prepare the hydrochloride, 1.5 mL of a 2.9 molar ethanolichydrochloric acid solution was added dropwise. The precipitate wasfiltered off, washed twice with 1-mL portions of ethanol and then dried.

a) 2,5-Diamino-1-(4-nirophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-nitrobenzene

Yield: 0.025 g (80% of the theoretical)

Mass spectrum MH⁺: 230 (100)

b) 2,5-Diamino-1-(4-chlorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-chlorobenzene

Yield: 0.025 g (86% of the theoretical)

Mass spectrum MH⁺: 219 (100)

c) 2,5-Diamino-1-(4-trifluoromethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-trifluoromethylbenzene

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 253 (100)

d) 2,5-Diamino-1-(4-cyanophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-cyanobenzene

Yield: 0.025 g (90% of the theoretical)

Mass spectrum MH⁺: 210 (100)

e) 2,5-Diamino-1-(4-methylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-methylbenzene

Yield: 0.025 g (92% of the theoretical)

Mass spectrum MH⁺: 199 (100)

f) 2,5-Diamino-1-(4-hydroxyphenyl)benzene Dihydrochloride

Bromo derivative used: 4-bromophenol

Yield: 0.025 g (92% of the theoretical)

Mass spectrum MH⁺: 201 (100)

g) 2,5-Diamino-1-(4-aminophenyl)benzene Dihydrochloride

Bromo derivative used: 4-bromoaniline

Yield: 0.025 g (90% of the theoretical)

Mass spectrum MH⁺: 200 (100)

h) 2,5-Diamino-1-(4-ethylcarboxyphenyl)benzene Dihydrochloride

Bromo derivative used: ethyl 1-bromobenzoate

Yield: 0.025 g (75% of the theoretical)

Mass spectrum MH⁺: 257 (100)

i) 2,5-Diamino-1-(3-nitro-4-trifluoromethyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-nitro-4-trifluoromethylbenzene

Yield: 0.025 g (65% of the theoretical)

Mass spectrum MH⁺: 298 (100)

j) 2,5-Diamino-1-phenoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-phenoxybenzene

Yield: 0.025 g (70% of the theoretical)

Mass spectrum MH⁺: 277 (100)

k) 2,5-Diamino-1-(2-methoxy-5-cyanophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-methoxy-5-cyanobenzene

Yield: 0.025 g (80% of the theoretical)

Mass spectrum MH⁺: 240 (100)

l) 2,5-Diamino-1-(3-nitro-4-methylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-nitro-4-methylbenzene

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 244 (100)

m) 2,5-Diamino-1-(2-nitro-4-methylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-nitro-4-methylbenzene

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 244 (100)

n) 2,5-Diamino-1-(3-trifluoromethyl-4-nitrophenyl)benzeneDihydrochloride

Bromo derivative used: 1-bromo-3-trifluoromethyl-4-nitrobenzene

Yield: 0.025 g (67% of the theoretical)

Mass spectrum MH⁺: 298 (100)

o) 2,5-Diamino-1-(2,4-dimethoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,4-dimethoxybenzene

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 245 (100)

p) 2,5-Diamino-1-(2-methyl-3-nitrophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-methyl-3-nitrobenzene

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 244 (100)

q) 2,5-Diamino-1-(3,4-dimethoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3,4-dimethoxybenzene

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 245 (100)

r) 2,5-Diamino-1-(2,5-dimethoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,5-dimethoxybenzene

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 245 (100)

s) 2,5-Diamino-1-(2-methyl-4-nitrophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-methyl-4-nitrobenzene

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 244 (100)

t) 2,5-Diamino-1-(2-methyl-5-nitrophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-methyl-5-nitrobenzene

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 244 (100)

u) 2,5-Diamino-1-[4-(1-oxypentyl)phenyl]benzene Dihydrochloride

Bromo derivative used: 1-(4-bromophenyl)-1-pentan-1-one

Yield: 0.025 g (78% of the theoretical)

Mass spectrum MH⁺: 269 (100)

v) 2,5-Diamino-3-fbiphenyl)benzene Dihydrochloride

Bromo derivative used: 3-bromophenyl

Yield: 0.025 g (76% of the theoretical)

Mass spectrum MH⁺: 261 (100)

w) 2,5-Diamino-1-(2,5-dimethylphenyl)benzene

Bromo derivative used: 1-bromo-2,5-dimethylbenzene

Yield: 0.025 g (89% of the theoretical)

Mass spectrum MH⁺: 213 (100)

x) 2,5-Diamino-1-(2-chloro-5-nitrophenyl)benzene Dihydrochlodde

Bromo derivative used: 1-bromo-2-chloro-5-nitrobenzene

Yield: 0.025 g (73% of the theoretical)

Mass spectrum MH⁺: 265 (100)

y) 2,5-Diamino-1-(2-methyl-4-hydroxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-methyl-4-hydroxybenzene

Yield: 0.025 g (86% of the theoretical)

Mass spectrum MH⁺: 215 (100)

z) 2,5-Diamino-1-(indan-1-on-5-yl)benzene Dihydrochloride

Bromo derivative used: 5-bromo-1-1-indanone

Yield: 0.025 g (80% of the theoretical)

Mass spectrum MH⁺: 239 (100)

a′) 2,5-Diamino-1-(2-methylmethoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-methyl-4-methoxybenzene

Yield: 0.025 g (83% of the theoretical)

Mass spectrum MH⁺: 229 (100)

b′) 2,5-Diamino-1-(2,4-dichlorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,4-dichlorobenzene

Yield: 0.025 g (77% of the theoretical)

Mass spectrum MH⁺: 253 (100)

c′) 2,5-Diamino-1-(2,3-methylenedioxyphenyl]benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,3-methylenedioxybenzene

Yield: 0.025 g (83% of the theoretical)

Mass spectrum MH⁺: 229 (100)

d′) 2.5-Diamino-1-(3-trifluoromethyl-4-chlorophenyl)benzeneDihydrochloride

Bromo derivative used: 1-bromo-3-trifluoromethyl-4-chlorobenzene

Yield: 0.025 g (70% of the theoretical)

Mass spectrum MH⁺: 287 (100)

e′) 2,5-Diamino-1-(3,5-dimethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3,5-dimethylbenzene

Yield: 0.025 g (88% of the theoretical)

Mass spectrum MH⁺: 213 (100)

f′) 2,5-Diamino-1-(3,4-dimethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3,4-dimethylbenzene

Yield: 0.025 g (88% of the theoretical)

Mass spectrum MH⁺: 212 (100)

g′) 2,5-Diamino-1-(3-chlorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-chlorobenzene

Yield: 0.025 g (86% of the theoretical)

Mass spectrum MH⁺: 219 (100)

h′) 2,5-Diamino-1-(3-trifluoromethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-trifluoromethylbenzene

Yield: 0.025 g (77% of the theoretical)

Mass spectrum MH+(+CH₃CN): 294 (100)

i′) 2,5-Diamino-1-(2-methoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-methoxybenzene

Yield: 0.025 g (87% of the theoretical)

Mass spectrum MH⁺: 215 (100)

j′) 2,5-Diamino-1-(4-ethoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-ethoxybenzene

Yield: 0.025 g (83% of the theoretical)

Mass spectrum MH⁺: 229 (100)

k′) 2,5-Diamino-1-(4-fluorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-fluorobenzene

Yield: 0.025 g (91% of the theoretical)

Mass spectrum MH⁺: 203 (100)

l′) 2,5-Diamino-1-(carboxamidophenyl)benzene Dihydrochloride

Bromo derivative used: 4-bromobenzamide

Yield: 0.025 g (83% of the theoretical)

Mass spectrum MH⁺: 228 (100)

m′) 2,5-Diamino-1-(2-nitro-4-methoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-nitro-4-methoxybenzene

Yield: 0.025 g (75% of the theoretical)

Mass spectrum MH⁺: 260 (100)

n′) 2,5-Diamino-1-(1-acetyl-2,3-dihydroindol-5-yl)benzeneDihydrochloride

Bromo derivative used: 1-acetyl-2,3-dihydro-5-bromoindol

Yield: 0.025 g (73% of the theoretical)

Mass spectrum MH⁺: 268 (100)

o′) 2,5-Diamino-1-(2,4-dimethoxy-3-carboxamidophenyl)benzeneDihydrochloride

Bromo derivative used: 3-bromo-2,6-dimethoxybenzamide

Yield: 0.025 g (69% of the theoretical)

Mass spectrum MH⁺: 288 (100)

p′) 2,5-Diamino-1-(2-chloro-4-nitrophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-chloro-4-nitrobenzene

Yield: 0.025 g (74% of the theoretical)

Mass spectrum MH⁺: 264 (100)

q′) 2,5-Diamino-1-(2,5-difluoro-4-nitrophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,5-difluoro-4-nitrobenzene

Yield: 0.025 g (74% of the theoretical)

Mass spectrum MH⁺: 266 (100)

r′) 2,5-Diamino-1-(2-chloro-4-N-acetylaminophenyl)benzeneDihydrochloride

Bromo derivative used: 4-bromo-2-chloroacetanilide

Yield: 0.025 g (72% of the theoretical)

Mass spectrum MH⁺: 276 (100)

s′) 2,5-Diamino-1-(indol-5-yl)benzene Dihydrochloride

Bromo derivative used: 1-bromoindol

Yield: 0.025 g (84% of the theoretical)

Mass spectrum MH⁺: 224 (100)

t′) 2,5-Diamino-1-(3,5-dichlorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3,5-dichloropbenzene

Yield: 0.025 g (77% of the theoretical)

Mass spectrum MH⁺: 253 (100)

u′) 2,5-Diamino-1-(2,4,5-trimethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,4,5-trimethylbenzene

Yield: 0.025 g (84% of the theoretical)

Mass spectrum MH⁺: 227 (100)

v′) 2,5-Diamino-1-(2,4-dimethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,4-dimethylbenzene

Yield: 0.025 g (88% of the theoretical)

Mass spectrum MH⁺: 213 (100)

w′) 2,5-Diamino-1-(2,3-dimethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,3-dimethylbenzene

Yield: 0.025 g (88% of the theoretical)

Mass spectrum MH⁺: 213 (100)

x′) 2,5-Diamino-1-(3-fluorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-fluorobenzene

Yield: 0.025 g (91% of the theoretical)

Mass spectrum MH⁺: 203 (100)

y′) 2,5-Diamino-1-(3-cyanophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-cyanobenzene

Yield: 0.025 g (89% of the theoretical)

Mass spectrum MH⁺: 210 (100)

z′) 2,5-Diamino-1-(3-methylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-methylbenzene

Yield: 0.025 g (92% of the theoretical)

Mass spectrum MH⁺: 199 (100)

a″) 2,5-Diamino-1-(3-hydroxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-hydroxybenzene

Yield: 0.025 g (92% of the theoretical)

Mass spectrum MH⁺: 201 (100)

b″) 2,5-Diamino-1-(3-aminomethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-aminomethylbenzene

Yield: 0.025 g (77% of the theoretical)

Mass spectrum MH⁺: 214 (100)

c″) 2,5-Diamino-1-(3-carboxythylphenyl)benzene Dihydrochloride

Bromo derivative used: ethyl 3-bromobenzoate

Yield: 0.025 g (76% of the theoretical)

Mass spectrum MH⁺: 257 (100)

d″) 2,5-Diamino-1-(2-nitrophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-nitrobenzene

Yield: 0.025 g (83% of the theoretical)

Mass spectrum MH⁺: 230 (100)

e′) 2,5-Diamino-1-(2-fluorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-fluorobenzene

Yield: 0.025 g (91% of the theoretical)

Mass spectrum MH⁺: 203 (100)

f″) 2,5-Diamino-1-(2-chlorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-chlorobenzene

Yield: 0.025 g (86% of the theoretical)

Mass spectrum MH⁺: 219 (100)

g″) 2,5-Diamino-1-(2-trifluoromethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-trifluoromethylbenzene

Yield: 0.025 g (77% of the theoretical)

Mass spectrum MH⁺: 253 (100)

h″) 2,5-Diamino-1-(2-methylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-methylbenzene

Yield: 0.025 g (92% of the theoretical)

Mass spectrum MH⁺: 199 (100)

i″) 2,5-Diamino-1-(2-cyanomethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-cyanomethylbenzene

Yield: 0.025 g (84% of the theoretical)

Mass spectrum MH⁺: 224 (100)

j″) 2,5-Diamino-1-(4-ethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-ethyl)benzene

Yield: 0.025 g (88% of the theoretical)

Mass spectrum MH⁺: 213 (100)

k″) 2,5-Diamino-1-(4-propylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-propyl)benzene

Yield: 0.025 g (84% of the theoretical)

Mass spectrum MH⁺: 227 (100)

l″) 2,5-Diamino-1-(4 isopropylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-isopropylbenzene

Yield: 0.025 g (84% of the theoretical)

Mass spectrum MH⁺: 227 (100)

m″) 2,5-Diamino-1-(4-butylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-butylbenzene

Yield: 0.025 g (80% of the theoretical)

Mass spectrum MH⁺: 241 (100)

n″) 2,5-Diamino-1-(4-tert.butylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-tert.butylbenzene

Yield: 0.025 g (80% of the theoretical)

Mass spectrum MH⁺: 241 (100)

o″) 2,5-Diamino-1-(4-pentylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-pentylbenzene

Yield: 0.025 g (76% of the theoretical)

Mass spectrum MH⁺: 255 (100)

p″) 2,5-Diamino-1-(4-acetylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-acetylbenzene

Yield: 0.025 g (84% of the theoretical)

Mass spectrum MH⁺: 227 (100)

q″) 2,5-Diamino-1-(4-thiomethoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-thiomethoxybenzene

Yield: 0.025 g (91% of the theoretical)

Mass spectrum MH⁺: 203 (100)

r″) 2,5-Diamino-1-(2-ethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-ethylbenzene

Yield: 0.025 g (88% of the theoretical)

Mass spectrum MH⁺: 213 (100)

s″) 2,5-Diamino-1-(2-fluoro-4-methylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-fluoro-4-methylbenzene

Yield: 0.025 g (86% of the theoretical)

Mass spectrum MH⁺: 217 (100)

t″) 2,5-Diamino-1-(2-methyl-5-fluorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-methyl-5-fluorobenzene

Yield: 0.025 g (86% of the theoretical)

Mass spectrum MH⁺: 217 (100)

u″) 2,5-Diamino-1-(2-thiomethoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-thiomethoxybenzene

Yield: 0.025 g (82% of the theoretical)

Mass spectrum MH⁺: 231 (100)

v″) 2,5-Diamino-1-(2,3-dichlorophenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,3-dichlorobenzene

Yield: 0.025 g (77% of the theoretical)

Mass spectrum MH⁺: 253 (100)

w″) 2,5-Diamino-4-(4′-hydroxybiphenyl)benzene Dihydrochloride

Bromo derivative used: 4-bromo-4′-hydroxybiphenyl

Yield: 0.025 g (72% of the theoretical)

Mass spectrum MH⁺: 277 (100)

x″) 2,5-Diamino-1-(3-ethoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-ethoxybenzene

Yield: 0.025 g (77% of the theoretical)

Mass spectrum MH⁺: 229 (100)

y″) 2,5-Diamino-1-([42-pyrrolidin-1-ylethoxy)phenyl]benzeneDihydrochloride

Bromo derivative used: 1-bromo-4-(2-pyrrolidin-1-ylethoxy)benzene

Yield: 0.025 g (61% of the theoretical)

Mass spectrum MH⁺: 298 (100)

z″) 2,5-Diamino-1-([4-(1-hydroxyethyl)phenyl]benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-(1-hydroxyethyl)benzene

Yield: 0.025 g (83% of the theoretical)

Mass spectrum MH⁺: 229 (100)

a″′) 2,5-Diamino-1-(2,4-trifluoromethylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2,4-trifluoromethylbenzene

Yield: 0.025 g (64% of the theoretical)

Mass spectrum MH⁺: 321 (100)

b ″′) 2,5-Diamino-1-(2-fluoro-5-acetylphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-fluoro-5-acetylbenzene

Yield: 0.025 g (79% of the theoretical)

Mass spectrum MH⁺: 245 (100)

c″′) 2,5-Diamino-1-(3-fluoro-4-methoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-fluoro-4-methoxybenzene

Yield: 0.025 g (82% of the theoretical)

Mass spectrum MH⁺: 233 (100)

d″′) 2,5-Diamino-1-(3-acetyl-4hydroxyphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-acetyl-4-hydroxybenzene

Yield: 0.025 g (79% of the theoretical)

Mass spectrum MH⁺: 243 (100)

e″′) 2,5-Diamino-1-[4-(2-hydroxyethyl)phenyl]benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-(2-hydroxyethyl)benzene

Yield: 0.025 g (79% of the theoretical)

Mass spectrum MH⁺: 245 (100)

f″′) 2,5-Diamino-1-[4-(propyl-1-one)phenyl]benzene Dihydrochloride

Bromo derivative used: 1-bromo-4-(propyl-1-one)benzene

Yield: 0.025 g (80% of the theoretical)

Mass spectrum MH⁺: 241 (100)

g″′) 2,5-Diamino-1-(4-N,N-diisopropylaminomethylphenyl)benzeneDihydrochloride

Bromo derivative used: 1-bromo-4-N,N-diisopropylaminomethylbenzene

Yield: 0.025 g (61% of the theoretical)

Mass spectrum MH⁺: 298 (100)

h″′) 2,5-Diamino-1-(3-acetyiphenyl)benzene Dihydrochloride

Bromo derivative used: 1-bromo-3-acetylbenzene

Yield: 0.025 g (84% of the theoretical)

Mass spectrum MH⁺: 227 (100)

i″′) 2,5-Diamino-1-[2-(2-hydroxyethyl)phenyl]benzene Dihydrochloride

Bromo derivative used: 1-bromo-2-(2-hydroxyethyl)benzene

Yield: 0.025 g (83% of the theoretical)

Mass spectrum MH⁺: 229 (100)

j″′) 2,5-Diamino-1-(4-methoxyphenyl)benzene Dihydrochloride

Bromo derivative used: 4-bromoanisole

Yield: 0.025 g (87% of the theoretical)

Mass spectrum MH⁺: 215 (100)

Example 2 Synthesis of 2,5-Diamino-4-methoxy-1-phenylbenzene. 2 HCl

A) Synthesis of 2-Amino-4-methoxy-5-nitro-1-phenylbenzene

2.02 g (0.01 mole) of 4-chloro-5-nitro-2-aminoanisole and 0.013 mole ofphenylboric acid were dissolved in 70 mL of 1,2-dimethoxyethane underargon. Then, 0.5 g (0.0005 mole) oftetrakis(triphenylphosphine)palladium and 13 mL of 2 N potassiumcarbonate solution were added, and the reaction mixture was heated to80° C. At the end of the reaction, the reaction mixture was poured into100 mL of ethyl acetate. The organic phase was extracted with dilutesodium hydroxide solution and then dried over magnesium sulfate. Thesolvent was distilled off from a rotary evaporator, and the residue waspurified [by column chromatography] on silica gel using hexane/ethylacetate (8:1) [as the eluent].

Yield: 1.54 g (63% of the theoretical)

M.p.: 105-109° C. (yellow crystals)

B. Synthesis of 2,5-Diamino-4-methoxy-1-phenylbenzene.2 HCl

0.5 g (2-mmoles) of 2-amino-4-methoxy-5-nitro-1-phenylbenzene (A) wasdissolved in 30 mL of ethanol and after addition of 100 mg of apalladium-on-active carbon catalyst (10%) hydrogenated at 25° C. Afterthe theoretical amount of hydrogen had been absorbed, the catalyst wasfiltered off and excess dilute hydrochloric acid was added to thefiltrate. The solution was evaporated in a rotary evaporator, afterwhich the precipitated hydrochloride was filtered off and dried.

Yield: 0.53 g (93% of the theoretical)

M.p.: 257-260° C. (colorless crystals)

CHN analysis (C₁₃H₁₆N₂OCl₂) % C % H % N Calcd. 54.37 5.62 9.75 Found54.09 5.42 9.62

Example 3 Synthesis of 2,5-Diamino-4-methyl-1-phenylbenzene. 2 HCl

A. Synthesis of 2-Amino-4-methyl-5-nitro-1-phenylbenzene

1.87 g (0.01 mole) of 5-chloro-2-methyl-4-nitroaniline and 0.013 mole ofphenylboric acid were dissolved in 70 mL of 1,2-dimethoxyethane underargon. Then, 0.5 g (0.0005 mole) oftetrakis(triphenylphosphine)palladium and 13 mL of 2 N potassiumcarbonate solution were added, and the reaction mixture was heated to80° C. At the end of the reaction, the reaction mixture was poured into100 mL of ethyl acetate. The organic phase was extracted with dilutesodium hydroxide solution and then dried over magnesium sulfate. Thesolvent was distilled off from a rotary evaporator, and the residue waspurified [by column chromatography] on silica gel using hexane/ethylacetate (8:1) [as the eluent].

Yield: 2.05 g (90% of the theoretical)

NMR

(500 MHz, CDCl₃) 7.82 (s. 1H); 7.4-7.3 (m, 3H); 7.2 (d, 2H); 6.45 (s,1H); 6.3 (s, 2H); 2.13 (s, 3H).

B. Synthesis of 2.5-Diamino-4-methyl-1-phenylbenzene.2 HCl 0.5 g(2-mmoles) of 2-amino-4-methyl-5-nitro-1-phenylbenzene (A) was dissolvedin 30 mL of ethanol and after addition of 100 mg of apalladium-on-active carbon catalyst (10%) hydrogenated at 25° C. Afterthe theoretical amount of hydrogen had been absorbed, the catalyst wasfiltered off and excess dilute hydrochloric acid was added to thefiltrate. The solution was evaporated in a rotary evaporator, afterwhich the precipitated hydrochloride was filtered off and dried.

Yield: 0.50 g (93% of the theoretical)

M.p.: 263-265° C. (colorless crystals)

CHN analysis (C₁₃H₁₆N₂Cl₂) % C % H % N Calcd. 54.37 5.62 9.75 Found54.09 5.42 9.62

Example 4 Synthesis of 2-Alkylamino-5-amino-1-phenylbenzenes of GeneralFormula (I). (General Method of Synthesis)

A) Synthesis of 2-Fluoro-5-nitro-1-phenylbenzene

1.75 g (0.01 mole) of 3-chloro-4-fluoronitrobenzene and 0.013 mole ofphenylboric acid were dissolved in 70 mL of 1,2-dimethoxyethane underargon. Then, 0.5 g (0.0005 mole) oftetrakis(triphenylphosphine)palladium and 13 mL of 2N potassiumcarbonate solution were added, and the reaction mixture was heated to80° C. At the end of the reaction, the reaction mixture was poured into100 mL of ethyl acetate. The organic phase was extracted with dilutesodium hydroxide solution and then dried over magnesium sulfate. Thesolvent was distilled off from a rotary evaporator, and the residue waspurified [by column chromatography] on silica gel using hexane/toluene(10:1) [as the eluent].

Yield: 2.05 g (94% of the theoretical)

NMR

(250 MHz, CDCl₃) 8.39 (dd, 1H); 8.25-8.21 (m, 1H); 7.57 (d, 2H);7.5-7.46 (m, 3H); 7.31 (t, 1H).

B) Synthesis of 2-Alkylamino-5-nitro-1-phenylbenzene of Formula (I).

(General Method of Synthesis)

2.2 g (0.01 mole) of 2-fluoro-5-nitro-1-phenylbenzene (A) was dissolvedin 25 mL of ethanol. Then, 0.05 mole of the desired amine was added atreflux. At the end of the reaction, the reaction mixture was poured intowater and the aqueous phase was extracted with ethyl acetate. Theorganic phase was dried over magnesium sulfate. The solvent wasdistilled off from a rotary evaporator, and the residue was purified [bycolumn chromatography] over silica gel using hexane/ethyl acetate (20:1)[as the eluent].

a) 2-Dimethylamino-5-nitro-1-phenylbenzene

Amine used: dimethylamine

Yield: 2.1 g (87% of the theoretical)

M.p.: 70-73° C. (yellow crystals)

b) 2-Di-(2-hydroxyethyl)amino-5-nitro-1-phenylibenzene

Amine used: diethanolamine

Yield: 0.5 g (18% of the theoretical)

Orange-colored oil

NMR

(500 MHz, CDCl₃): 8.13 (dd, 1H); 8.06 (d, 1H); 7.47-7.26 (m, 6H);3.6-3.58 (m, 4H); 3.3-3.27 (m, 4H).

c) 2-Pyrrolidino-5-nitro-1-phenylbenzene

Amine used: pyrrolidine

Yield: 2.5 g (93% of the theoretical)

M.p.: 109-113° C. (yellow crystals)

d) 2-(2-Hydroxyethyl)amino-5-nitro-1-phenylbenzene

Amine used: ethanolamine

Yield: 2.5 g (96% of the theoretical)

Orange-colored oil

NMR

(500 MHz, CDCl₃): 8.14 (dd, 1H); 8.00 (s, 1H); 7.5-7.4 (m, 5H); 6.67 (d,1H); 5.1 (s, 1H); 3.84-3.82 (dd, 2H); 3.4-3.37 (dd, 2H).

e) 2-(2-Methoxyethyl)amino-5-nitro-1-phenylbenzene

Amine used: 2-methoxyethylamine

Yield: 2.6 g (96% of the theoretical)

M.p.: 93-95° C. (yellow crystals)

f) 2-(2,3-Dihydroxypropyl)amino-5-nitro-1-phenylbenzene

Amine used: 2,3-dihydroxypropylamine

Yield: 2.6 g (90% of the theoretical)

M.p.: 127-131° C. (orange crystals)

C. Synthesis of 2-Alkylamino-1-phenylbenzenes of General Formula (I).

(General Method of Synthesis)

2-mmoles of 2-alkylamino-5-nitro-1-phenylbenzene (B) was dissolved in 30mL of ethanol and after addition of 100 mg of a palladium-on-activecarbon catalyst (10%) hydrogenated at 25° C. After the theoreticalamount of hydrogen had been absorbed, the catalyst was filtered off andexcess dilute hydrochloric acid was added to the filtrate. The solutionwas evaporated in a rotary evaporator, after which the precipitatedhydrochloride was filtered off and dried.

a) 2-Di-(2-dimethylamino-5-amino-1-phenylbenzene Dihydrochloride

Yield: 0.33 g (77% of the theoretical)

M.p.: 220-225° C. (colorless crystals)

CHN analysis (C₁₄H₁₈N₂Cl₂) % C % H % N Calcd. 58.96 6.36 9.82 Found58.75 6.43 9.61

b) 2-Di-(2-hydroxyethyl)amino-5-amino-1-phenylbenzene Dihydrochloride

Yield: 0.6 g (80% of the theoretical)

M.p.: 222-225° C. (colorless crystals)

CHN analysis (C₁₆H₂₂N₂O₂Cl₂) % C % H % N Calcd. 55.66 6.42 8.11 Found55.21 6.21 7.96

c) 2-Pyrrolidino-5-amino-1-phenylbenzene Dihydrochloride

Yield: 0.41 g (87% of the theoretical)

M.p.: 256-261° C. (colorless crystals)

CHN analysis (C₁₆H₂₀N₂Cl₂) % C % H % N Calcd. 61.74 6.48 9.00 Found61.00 6.81 8.65

d) 2-(2-Hydroxyethyl)amino-5-amino-1-phenylbenzene Dihydrochloride

Yield: 0.47 g (92% of the theoretical)

M.p.: 210-213° C. (colorless crystals)

CHN analysis (C₁₄H₁₈N₂OCl₂) % C % H % N Calcd. 55.83 6.02 9.30 Found55.71 6.25 9.43

e) 2-(2-Methoxyethyl)amino-5-amino-1-phenylbenzene Dihydrochloride

Yield: 0.47 g (94% of the theoretical)

M.p.: 74° C. (decomposition) (colorless crystals)

CHN analysis (C₁₅H₂₀N₂OCl₂) % C % H % N Calcd. 57.15 6.39 8.89 Found56.82 7.04 8.63

f) 2-(2,3-Dihydroxypropyl)amino-5-amino-1-phenylbenzene Dihydrochloride

Yield: 0.48 g (90% of the theoretical)

Colorless oil

CHN analysis (C₁₅H₂₀N₂O₂Cl₂ × H₂O) % C % H % N Calcd. 51.58 6.35 8.02Found 52.18 6.8 7.87

Examples 5 to 8

Hair Colorants

Hair colorants solutions of the following composition were prepared:

0.00125 mole of developer of formula (I) according to Table 1 0.00125mole of coupler according to Table 1 10.0 g of potassium oleate (8%aqueous solution) 10.0 g of ammonia (22% aqueous solution) 10.0 g ofisopropanol 0.3 g of ascorbic acid to 100.0 g water

Immediately before use, 30 g of the foregoing colorant solution wasmixed with 30 g of 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 min at 40° C.,the hair was rinsed with water, washed with a commercial shampoo anddried. The resulting color shades are shown in Table 1.

TABLE 1 DEVELOPER OF SHADE EXAMPLE FORMULA (I) COUPLER OBTAINED 52,5-diamino-1- 2-amino-4-(2′-hy- dark-blue phenylbenzene.2droxyethyl)amino- HCl anisole sulfate 6 2,5-diamino-1- resorcinoldark-blond phenylbenzene.2 HCl 7 2,5-diamino-4- resorcinol dark blondmethyl-1-phenyl- benzene 8 2-di(2-hydroxy- 2-amino-4-(2- blueethyl)amino-5- hydroxyethyl) amino-1-phenyl- aminoanisole benzene.2HClsulfate

Examples 9 to 14

Hair Colorants

Hair colors solutions of the following composition were prepared:

0.00125 mole of developer of formula (I) according to Table 2 0.00125mole of coupler according to Table 2 1.000 g of potassium oleate (8%aqueous solution) 1.000 g of ammonia (22% aqueous solution) 1.000 g ofethanol 0.300 g of ascorbic acid to 100 g water

Immediately before use, 10 g of the foregoing colorant solution wasmixed with 10 g of 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 min at 40° C.,the hair was rinsed with water, washed with a commercial shampoo anddried. The resulting color shades are shown in Table 2.

TABLE 2 DEVELOPER OF SHADE EXAMPLE FORMULA (I) COUPLER OBTAINED 92,5-diamino-1-(hy- 1,3-diamino-4-(2-hy- dark-blue droxy)phenylben-droxyethoxy)benzene zene.2HCl 10 2,5-diamino-1-(4- resorcinol dark-blondaminophenyl)ben- zene 11 2,5-diamino-1-(2- resorcinol dark-blondmethyl-4-hydroxy- phenyl)benzene. 2 HCl 12 2,5-diamino-1-(4-1,3-diamino-4-(2-hy- dark-blue fluorophenyl)ben- droxyethoxy)benzenezene.2 HCl 13 2,5-diamino-1-(3- resorcinol dark-blond methylphenyl)ben-zene.2 HCl 14 2,5-diamino-1-(3- 1,3-diamino-4-(2-hy- dark-bluefluoro-4-methoxy- droxyethoxy)benzene phenyl)benzene 2. HCl

Example 15

Hair Colorant

A hair colorant solution of the following composition was prepared:

0.160 g of 2,5-diamino-1-phenylbenzene.2 HCl 0.160 g of1,4-diamino-2-(2-hydroxyethyl)benzene sulfate 0.137 g of1,3-dihydroxybenzene 0.100 g of 1,3-dihydroxy-2-methylbenzene 0.100 g of2-amino-5-methylphenol 10.000 g of potassium oleate (8% aqueoussolution) 10.000 g of ammonia (22% aqueous solution) 10.000 g ofisopropanol 0.300 g of ascorbic acid to 100.000 g water

Immediately before use, 30 g of the foregoing colorant solution wasmixed with 30 g of 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 min at 40° C.,the hair was rinsed with water, washed with a commercial shampoo anddried. The hair had a blond shade.

Example 16

Hair Colorant

A hair colorant solution of the following composition was prepared:

0.320 g of 2,5-diamino-1-phenylbenzene.2 HCl 0.300 g of5-amino-2-methylphenol 0.600 g of 4-amino-3-methylphenol 0.600 g of4-aminophenol 0.100 g of α-naphthol 0.200 g of2-chloro-6-(ethylamino)-4-nitrophenol 10.000 g of potassium oleate (8%aqueous solution) 10.000 g of ammonia (22% aqueous solution) 10.000 g ofisopropanol 0.300 g of ascorbic acid to 100.000 g water

Immediately before use, 30 g of the foregoing colorant solution wasmixed with 30 g of 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 min at 40° C.,the hair was rinsed with water, washed with a commercial shampoo anddried. The hair had a red shade.

Example 17

Hair Colorant

A hair colorant solution of the following composition was prepared:

0.320 g of 2,5-diamino-1-phenylbenzene.2 HCl 0.040 g of5-amino-2-methylphenol 0.090 g of 2-amino-(2′-hydroxyethyl)aminoanisolesulfate 0.030 g of 3-aminophenol 0.030 g of 1,3-dihydroxybenzene 0.040 gof 1,3-dihydroxy-5-methylbenzene 0.100 g of 4-amino-5-methylphenol 0.002g of 2-amino-3-methylphenol 0.100 g of 2-amino-6-methylphenolhydrochloride 0.010 g of 4-chloro-N-(2-hydroxyethyl)-2-nitroaniline0.020 g of 2-amino-4,6-dinitrophenol 0.100 g of2-chloro-6-(ethylamino)-4-nitrophenol 10.000 g of potassium oleate (8%aqueous solution) 10.000 g of ammonia (22% aqueous solution) 10.000 g ofisopropanol 0.300 g of ascorbic acid to 100.000 g water

Immediately before use, 30 g of the foregoing colorant solution wasmixed with 30 g of 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 min at 40° C.,the hair was rinsed with water, washed with a commercial shampoo anddried. The hair had a brown shade.

Example 18

Hair Colorant

A hair colorant solution of the following composition was prepared:

0.320 g of 2,5-diamino-1-phenylbenzene.2 HCl 0.040 g of5-amino-2-methylphenol 0.050 g of 1,3-diamino-4-(2-hydroxyethyl)benzene0.030 g of 3-aminophenol 0.030 of 1,3-dihydroxybenzene 0.040 g of1,3-dihydroxy-2-methylbenzene 0.100 g of 4-amino-5-methylphenol 0.200 gof 2-amino-3-methylphenol 0.100 g of 2-amino-6-methylphenolhydrochloride 0.010 g of 4-chloro-N-(2-hydroxyethyl)-2-nitroaniline0.020 g 2-amino-4,6-dinitrophenol 0.100 g2-chloro-6-(ethylamino)-4-nitrophenol 10.000 g of ammonia (22% aqueoussolution) 10.000 g of isopropanol 0.300 g of ascorbic acid to 100.000 gwater

Immediately before use, 30 g of the foregoing colorant solution wasmixed with 30 g of 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 min at 40° C.,the hair was rinsed with water, washed with a commercial shampoo anddried. The hair had a brown shade.

Example 19

Hair Colorant

A hair colorant solution of the following composition was prepared:

0.220 g of 2,5-diamino-1-phenylbenzene.2 HCl 0.100 g of1,4-diamino-2-(2-hydroxyethyl)benzene sulfate 0.020 g of5-amino-2-methylphenol 0.010 g of 1,3-diamino-4-(2-hydroxyethoxy)benzene0.004 g of 2-amino-4-(2′-hydroxyethyl)aminoanisole sulfate 0.020 g of1,3-dihydroxybenzene 0.040 g of 1,3-dihydroxy-2-methylbenzene 0.008 g of4-amino-3-methylphenol 10.000 g of potassium oleate (8%) aqueoussolution) 10.000 g of ammonia (22% aqueous solution) 10.000 g ofisopropanol 0.300 g of ascorbic acid to 100.000 g water

Immediately before use, 30 g of the foregoing colorant solution wasmixed with 30 g of 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 min at 40° C.,the hair was rinsed with water, washed with a commercial shampoo anddried. The hair had a brown shade.

Example 20

Hair Colorant

A hair colorant solution of the following composition was prepared:

0.220 g of 2,5-diamino-1-phenylbenzene.2 HCl 0.100 g of4-di-(2-hydroxyethyl)aminoaniline sulfate 0.020 g of5-amino-2-methylphenol 0.010 g of 1,3-diamino-4-(2-hydroxyethyl)benzene0.015 g 2-amino-4-(2′-hydroxyethyl)aminoanisole sulfate 0.020 g1,3-dihydroxybenzene 0.040 g of 1,3-dihydroxy-2-methylbenzene 0.008 g of4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole sulfate 10.000 g of potassiumoleate (8%) aqueous solution) 10.000 g of ammonia (22% aqueous solution)10.000 g of isopropanol 0.300 g of ascorbic acid to 100.000 g water

Immediately before use, 30 g of the foregoing colorant solution wasmixed with 30 g of 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 min at 40° C.,the hair was rinsed with water, washed with a commercial shampoo anddried. The hair had a brown shade.

Example 21

Hair Colorant

A hair colorant solution of the following composition was prepared:

0.320 g of 2,5-diamino-1-phenylbenzene.2 HCl 0.020 g of5-amino-2-methylphenol 0.010 g of 1,3-diamino-4-(2-hydroxyethoxy)benzene0.015 g of 2-amino-4-(2′-hydroxyethyl)aminoanisole sulfate 0.020 g of1,3-dihydroxybenzene 0.040 g of 1,3-dihydroxy-2-methylbenzene 0.008 g of4-amino-2-(aminomethyl)phenol dihydrochloride 10.000 g of potassiumoleate (8%) aqueous solution) 10.000 g of ammonia (22% aqueous solution)10.000 g of isopropanol 0.300 g of ascorbic acid to 100.000 g water

Immediately before use, 30 g of the foregoing colorant solution wasmixed with 30 g of 6% hydrogen peroxide solution. The mixture was thenapplied to bleached hair. After an exposure time of 30 min at 40° C.,the hair was rinsed with water, washed with a commercial shampoo anddried. The hair had a brown shade.

Unless otherwise indicated, all percentages are by weight.

What is claimed is:
 1. Coloring agent for the oxidative coloring of keratinic fibers based on a developer/coupler comibination, characterized in that it contains as the developer a 2,5-diamino-1-phenylbenzene derivative of general formula (I)

wherein R1, R2, R3 and R4 independently of each other denote hydrogen, a C1-C6 alkyl, C1-C4 hyroxyalkyl, C2-C4 dihydroxyalkyl or C1-C4 alkoxy-(C1-C4) alkyl group, or R1 and R2 or R3 and R4 form a four-membered to eight-membered aliphatic ring, with at least two of the R1 to R4 groups denoting hydrogen; R5 denotes hydrogen, a hydroxyl group, a halogen atom or a C1-C4 alkyl, C1-C4 hyroxyalkyl or C1-C4 alkoxy group; R6, R7, R8, R9 and R10 independently of each other denote hydrogen, a halogen atom or a cyano, hydroxyl, C1-C4 alkoxy, C1-C6 alkyl, C1-C4 alkyl thioether, mercapto, nitro, amino, alkylamino, dialkylamino, trifluoromethane, —C(OH), —C(O)CH3, —C(O)CF3, —Si(CH)3, C1-C4 hydroxyalkyl, C3-C4 dihydroxyalkyl, —CH═CHR11 or —(CH2)p-CO2R12 group or a —(CH2)p—R13 group, where p=1, 2, 3 or 4, or a —C(R14)═NR15 group or a C(R17)H—NR18R19 group, or two adjacent R6 to R10 groups form a —O—CH2—O bridge; with the proviso that at least one of R6 and R9 is not an amino group if R1, R2, R3 and R4 are hydrogen; R11 denotes hydrogen, a hydroxyl, nitro, amino, CO2R12 or —C(O)CH3 group; R12, R14 and R17 independently of each other denote hydrogen or a C1-C4 alky group; R13 denotes an amino or nitrile group; R15, R18 and R19 independently of each other denote hydrogen, a hydroxyl, C1-C4 alkyl, C1-C6 hydroxyalkyl or C3-C4 dihydroxyalkyl group or a radical of formula

 and R16 denotes hydrogen, an amino group or a hydroxyl group or a physiologically acceptable, water-soluble salt thereof.
 2. Coloring agent according to claim 1, characterized in that R5 denotes hydrogen.
 3. Coloring agent according to claim 1, characterized in that either both radicals R1 and R2 or both radicals R3 and R4 denote hydrogen.
 4. Coloring agent according to claim 1, characterized in that radicals R1 to R4 all denote hydrogen.
 5. Coloring agent according to claim 1, characterized in that four of the radicals R6 to R10 denote hydrogen and that the fifth of said radicals R6 to R10 denotes hydrogen, a —C(O)H group, a —C(O)CH3 group, a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group.
 6. Coloring agent according to claim 1, characterized in that the 2,5-diamino-1-phenylbenzene derivative of formula (I) is selected from among 2,5-diamino-1-phenylbenzene; 2,5-diamino-1-(3-nitrophenyl)bezene, 2,5-diamino-1-(4-methoxy-phenyl)benzene; 2,5-diamino-1-(3-methoxyphenyl)benzene; 2,5-diamino-1-(3-amino-phenyl)benzene; 2,5-diamino-1-(2-methylphenyl)benzene; 2,5-diamino-1-(3-methylphenyl)benzene; 2,5-diamino-1-(4-methylpheyl)benzene; 2,5-diamino-1-(3-chlorophenyl)benzene and 2,5-amino-1-(4-chlorophenyl)benzene, and physiologically acceptable salts thereof.
 7. Coloring agent according to claim 1, characterized in that it contains the diaminobenzene derivative of formula (I) in an amount from 0.005 to 20.0 wt %.
 8. Coloring agent according to claim 1, characterized in that it contains besides the 1,4-diaminobenzene derivative of formula (I) also at least one additional developer selected from among 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol, 4-aminophenol and derivatives thereof, 4,5-diaminopyrazol derivatives and tetraaminopyrimidines.
 9. Coloring agent according to claim 1, characterized in that it contains the developers and couplers in a total amount from 0.005 to 20.0 wt %, based on the total amount of oxidative coloring agent.
 10. Coloring agent according to claim 1, characterized in that it contains additionally at least one direct dye.
 11. Coloring agent according to claim 1, characterized in that it has a pH from 6.8 to 11.5.
 12. Coloring agent according to claim 1, characterized in that it is in the form of an aqueous or aqueous-alcoholic solution, a cream, a gel or an emulsion.
 13. Coloring agent according to claim 1, characterized in that it is a hair colorant.
 14. 2,5-Diamino-1-phenylbenzene derivatives of formula (I) according to claim 1 wherein at least one of radicals R1 to R10 is different from hydrogen, or physiologically tolerated water-soluble salts thereof. 